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Manganese-catalysed C-H functionalization of aromatic molecules

Project Description

C-H activation is en route to dramatically alter the way chemists make organic molecules with spectacular achievements over the last half decade. However, most advances have relied and still rely on the use of Pd-catalysts or other precious metals, with obvious sustainability issues: difficulty to apply to large scale synthesis, unreliability of the supply chain, large fluctuations on price, and the prospect of ‘running-out’ of the precious metal. Recently, Mn complexes have been shown to be able to mediate some C-H functionalisation processes in a ‘Pd-like’ manner, raising hopes that this could provide a robust alternative to current methods (Mn is the 3rd most abundant transition metal). However, lack of mechanistic understanding is hindering progress in the field, with most methods reported requiring harsh conditions (eg >100 °C) and showing low substrate scope. The successful candidate will apply state-of-the-art kinetic and organometallic mechanistic studies to the understanding of the current bottle-necks in Mn-catalysed C-H functionalisations. This knowledge will then be used to design new Mn-complexes capable of mild C-H activation methods with broadly applicable scope.

The student will receive training in organic synthesis, organometallic chemistry and in the design and development of complex multi-metallic catalytic cycles. Transferable skills such as reporting of results orally and in writing, time management, project planning and management will be developed.

Applicants are expected to hold, or about to obtain, a minimum upper second class undergraduate degree (or equivalent) in Chemistry subject area. A Masters degree in a relevant subject and/or experience is desirable.

Contact for further Information:
Prof. Igor Larrosa

Funding Notes

Funded by an EPSRC DTG and awarded by the School of Chemistry. The funding covers tuition fees and a stipend for 3.5 years (£14,777p.a. in 2018/19).
Open to UK/EU applicants only.
We expect the Programme to commence in September 2019.


“Cyclometallated ruthenium catalyst enables late-stage directed arylation of pharmaceuticals”, Marco Simonetti, Diego M. Cannas, Xavier Just-Baringo, Iñigo J. Vitorica-Yrezabal and Igor Larrosa Nature Chem. 2018, 10, 724-731.

“Benzoate cyclometallation enables oxidative addition of haloarenes at a Ru(II) center”, Marco Simonetti, Rositha Kuniyil, Stuart A. Macgregor and Igor Larrosa J. Am. Chem. Soc. 2018, 140, 11836–11847.

“Ag(I)-C–H Activation Enables Near-Room Temperature Direct α-Arylation of Benzo[b]thiophenes”, Chiara Colletto, Adyasha Panigrahi, Jaime Fernandez-Casado and Igor Larrosa J. Am. Chem. Soc. 2018, 140, 9638-9643

“Ag(I)-catalyzed C-H activation: the role of the Ag(I) salt in Pd/Ag mediated C-H arylation of electron-deficient arenes”, Daniel Whitaker, Jordi Burés and Igor Larrosa J. Am. Chem. Soc. 2016, 138, 8384-8387.

“Ru-Catalyzed C–H Arylation of Fluoroarenes with Aryl Halides”, Marco Simonetti, Gregory J. P. Perry, Xacobe C. Cambeiro, Francisco Juliá-Hernández, Jude N. Arokianathar and Igor Larrosa J. Am. Chem. Soc. 2016, 138, 3596-3606.

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